Lubricating composition



Patented Nov. 15, 1949 2,487,840 LUBRICATING COMPOSITION Paul R. Van Ess, Berkeley, Calif., assignor toShell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application May 19, 1947, Serial No. 749,079

(o1. 252-Vs2.7)

19 Claims.

This invention relates to new and novel products having properties of greatlyimproving and stabilizing lubricants. More particularly, this invention pertains to oleaginous materials, especially lubricants, such. as mineral lubricating oils, synthetic lubricants of hydrocarbon and nonhydrocarbon origin and the like, containing a multi-functional additive having detergent and anti-riugsticking properties, as well as acting as an inhibitor of oxidationand corrosion.

It is Well known that various lubricants, whether doped or undoped, tend to oxidize and form corrosive bodies and sludge when used in modern engines and machines operating under ordinary conditions, and especially at high speeds, elevated temperatures, heavy loads and other adverse conditions. Also as lubricants deteriorate during use, hard carbonaceous materials are formed on engine and machine parts, causing scratching and scuffing of movable metal parts and sticking of valves and piston rings in engines. In addition, known lubricants are generally incapable of maintaining a continuous lubricating film between movable metal parts; this results in a gradual or rapid wearing away of the metal parts. The damage thus caused requires replacement of such parts, or even a complete overhauling of engines and machines, resulting in expensive loss of production and time.

In the case of the highest quality non-corrosive, stable undoped mineral lubricating oils, which are highly refined for specific uses, or synthetic lubricants developed for special uses, it has been found that such oils and lubricants are generally highly susceptible to oxidation and deterioration, becoming progressively more and more corrosive in engines and machines even under ordinary operating conditions.

To improve the lubricating properties of oils and synthetic lubricants, it has become the practice to blend therewith one or more additives which have the effect or the property of inhibiting deterioration of lubricants and impart to them certain beneficial properties. Thus additives have been specifically designed which have the property of inhibiting corrosion of alloyed bearings such as copper-lead, cadmium-silver and the like, developed for automotive, Diesel and aircraft engines. Acidic oxidation or decomposition components formed in lubricants during use can readily attack these bearings, but are inhibited or prevented from doing this by the formation of a corrosion protective film formed with the aid of the additive on the bearing surface, Additives have .also been developed which possess the property of modifying the carbonaceous materials formed by deterioration of lubricants on piston rods, rings and valves and other metal parts in internal combustion engines, automotive and truck engines, aviation engines, high speed Diesel engines, and the like. These additives serve a very important function because by modifying this carbonaceous material so that it can be removed easily, the tendency of engine parts to become stuck is inhibited; ring sticking, piston scuffing andscratching and wearing away of other parts and material reduction of engine efficiency are thereby prevented.

. Other additives have been developed which act as detergents in order to assist in the removal of .soot, sludge, varnish, and/or lacquer formed from deterioration of the oil at high operating temperatures. Detergents, due to their cleansing action, prevent the build-up of these deleterious materials and assist in removing those formed.

.Anti-wear additiveshave the property of reducing friction of movable metal parts of the same or different metals. Due to the function exerted or property imparted by such additives on lubricants, wear caused by direct frictional contact of metals can be greatly reduced. Also, additives have been developed for withstanding extreme pressures, dispersion of impurities, solubilizing of certain other additives, etc.

The large number of additives thus developed has been due to the fact that an additive is capable of functioning mainly in only one specific manner: very few lubricant additives have the ability of improving a lubricant in more than just one respect. Thus a good anti-oxidant might not be able to inhibit lacquer and varnish formation on piston rods, or to act as a detergent or corrosion inhibitor. In many cases, it is found that whereas an additive possesses very good properties in one respect, this same additive is the cause of harmful deposits in another respect. A second and third additive is therefore frequently required in order to obtain a good stable lubricant. The combination of additives in lubricants wherein each additive exerts its influence without interfering with the function of other additives present is a difficult matter to attain because in most cases additives co-react or interfere with each other. To prevent this from occurring great care must be taken in selecting the additives,

'mixing them in specific proportions, and continuously watching and replacing additives which .have stopped functioning or have deteriorated.

It is an object of this invention to improve the product with a metal to form the salts.

' sure.

lubricants even under adverse operating condi-a tions. Still another object of this invention is .to use in lubricating compositions a material which prevents ring sticking as well as. the stickingiof other engine parts due todeterioration. of 1: the

lubricant. Also it is an object of this invention to use in lubricating compositions a material which inhibits wear, scufing, scratching .1.and other damage to engine parts. It is still another object of this invention to provide novel compounds which possessamulti-functional improving and enhancingiproperties whenadded to lubricants.

The above .and other objects. may-.be .attained in accordance with the present'inventionbyadd- .:ing to oleaginous materials, e. .g. various lubricating bases a minor amount :of a reaction productobtainedby treatingsaturated and unsaturated cyclic .ketonelfractions havingat least Y12 and preferably more than :18 carbon atoms in the molecule, said ketone ifractionsuhaving been derived from isophorone-bottoms during its synthesis fromacetoneby condensationas well .as

from other sources .witha sulfurizing agent and thereafter, if desired, treating said reaction ably, the sulfurizing agent-used toproduce the reaction products oft this invention may be. selected from the class consisting of-elemental sulfur, flowers ofsulfunsulfur halides, alkali polysulfides, ammonium hydrogensulfide-hydrogen sulfide, sulfur dioxide, etc. and the like. .The -preferred ketones used -to obtain the oil additive of this invention are the unsaturated cyclic ketones which are reacted with-these phosphorus sulfides and are :normally obtained from isophorone bottoms "produced by .condensation. of

acetone .under elevated temperature and pres- The isophoronebottoms thus produced may be fractionatedinto various' cuts each :of

-Whioh may be used to react'with arsulfurizing agent to'form the compound or oiladditive of 1 this .invention. Among the specific isophorone fractions which may be used to form the reaction product of this inventionare.toppedcrude isophorone, topped crude hydrolyzed isophorone bottoms, and the like. of the sulfurizing agent such as sulfur andcyclic ketones of this invention-may be varied over-wide Although the mol ratio limits, it is preferable to keep them within the range of from .521 to 1:1,respectively and preferably in the ratio of less than .5:1. The reaction between these two ingredients is generally carried out under controlledelevated temperature conditions.

The terms topped crude 'isophoronebottoms and topped crude hydrolyzed'isophorone bottoms,

and similar terms,-which-will-be hereinafter used and fully described are generic and-are used to identify various unsaturated cyclic ketone fractions of relatively high molecular Weight obtained from-acetone condensation. Unsaturated cyclic ketone fractions usable in reactions of the kind under consideration may be'obtained by condensing acetone in 30% to6()% caustic solution at a temperature ranging between'about "130 C.

Preferand 170 C., and under pressure of from 300 to 500 pounds per square inch. The resultant product is preferably subjected to distillation to remove distillable ketones and other constituents and impurities. The product remaining in the still is purified by filtration, solvent treatment, and comprises'crude unsaturated cyclic'ketones 'of high. molecular weight,:,.preferably. referred to as crude isophorone bottoms. The term iso- .10 r-phorone bottoms as referred to herein is thus a complex mixture of high molecular weight unsaturatedcyclic ketones containing at least 12 eandzpreferably more than 18 carbon atoms in the molecule. .The product formed is not to be con- 5- fused with-straight isophorone which is specifi- .cally 3,5,5tri1nethyl cyclohexene-Z-one-l, an unsaturated cyclic ketone containing only nine carbon atoms in the molecule. Isophorone bottoms-produced by condensation of acetone under conditions referred toiabove includes within its "scope any. and. allunsaturatedcyclic ketones conv.taining at least, 12 ;and.\preferably more than; .18 carbon atomsandhaving generally. .the chemical structural configuration: ofisophorone .as well v as the chemical configuration ,eresulting from its condensation.

Crude isophorcnesbottomslcan be fractionated and/or chemicallyitreated andeach fraction thereof can in turn :be: treated with. sulfur and the likeat elevated:temp'eratures. .wAmong the -various fractions which canobe obtained from crude isophoronelbottoms are stopped crude. isophorone bottomsawhichtcontain at .least. l5 carbonatoms .in the :moleculeiand. which .are obtained after removal'iof distillate .fromcrude isophorone bottoms 'to a. still zheadn temperature .of 140- C. at :mm. EHgapressure. .Crude-isophorone bottoms .cansbe subjected to; hydrolysis withdilutesodium hydroxide and the .acetone 1 and isophorone formed removed by distillation. The bottoms can -then .be' filtered and purified and comprise essentially unsaturated cyclic ketonescontaining-at least 12 and more carbon 1 atoms the: moleculeand are. referred toras crude hydrolyzed isophorone bottoms. This "material can be subjected-to Ldistillation to. split it =into 'two' -fractions. 'The .distilled hydrolyzed isophorone fraction -has:a,':boi1ing point ofiabout 140 C. at 10 mmF-Hg-pressureand.consists oha mixture of -unsaturated 'cyclic ketonescontaining between 15 .to- 18'carbon atoms in -themolecule. 3 The-residue 'is referred to: as J topped .crude hydrolyzed isophorone bottoms .and is similar to topped .crudeisophorone :bottoms. -They comprise essentially unsaturated cyclic ketones of at least 15 carbon atoms bathe-molecule. Crude isophorone bottoms can bealso subjected to condensation over solid sodium hydroxide' toyield two types of I resinous materials. 'The -first 60 resinous fraction V orsoft resin has a viscosity at "210 Fwof about 26 centist'okes'and an average molecular-weight of'320 to'350. The heavier fraction or medium resin has a-viscosity-at 210 of about 80*to120 centistokes -and an average molecular weight of 370' to 390. -All'of'the-yarious unsaturated cyclic-=ketone'fractions obtained in the manner -fully-'-desc'ribed above can be used for reacting with a sulfurizing'agent to form a multi-functional lubricating additive. 70 Other cyclic ketones having-'at-least 12 carbon atoms are obtained-by hydrogenating the-above unsaturated cyclic ketones-to obtain saturated cyclic ketones-having at least '12 carbon atoms, alkyl cyclohexanone, i: 'e.- dibut'yl cycl'ohexanone, 75'--alky1 -substituted -carvomerithone, -menthone,

pulegone, carvone, camphor, and the like having at least 12 carbon atoms.

Any suitable sulfurizing agent can be used in producing reaction products of this invention and. preferably elemental sulfur is used because of its availability, cost and desired reactivity.

The sulfurized cyclic ketone reaction products of this invention can be prepared from any of the ketone fractions obtained in the manner described above, although certain fractions are preferred to others. The kind of sulfurizing agent used, the ratio of the two reactants, the temperature, time and conditions under which the reaction is carried out, as well as the manner in which the final product is recovered, are also important and controlling factors. The preferred ketone fractions are topped crude isophorone bottoms which are residues remaining after removal of distillate from crude isophorone bottoms to a still head temperature of 140 C. at mm. Hg pressure, and comprise unsaturated cyclic ketones containing at least carbon atoms in the molecule. Another preferred fraction is topped crude hydrolyzed isophorone bottoms obtained from crude hydrolyzed isophorone bottoms similar to the topped crude isophorone bottoms. The term topped used throughout has the same meaning as in the petroleum art, namely, a distillation or fractionation step, whereby certain materials are removed as an overhead fraction.

The reaction temperature can be varied between about 130 C. and about 200 C. or higher, and preferably between 150 C. and 170 C. However, the initial or starting temperature should be controlled quite carefully and be restricted within relatively rather narrow limits to obtain a desired controlled reaction. If initially the reaction is allowed to progress at a rapid rate over 100" 0., due to the vigor of'the resultant reaction, it cannot then be controlled and an undesirable product forms. The initial stage of the reaction should be carefully controlled and heated slowly in a suitable bath or by any suitable means to an initial temperature of between about 60 C. and 80 C., and thereafter heated relatively more rapidly to the desired or optimum temperature.

The reaction should be carried out in substantially inert atmosphere and the two materials can be reacted per se or dispersed in a suitable inert or non-reactive diluent and then reacted under conditions described above. When the reaction is completed, the desired fraction can be extracted with a suitable material, such as non-aromatic hydrocarbons, e. g. one having a boiling range of between 164 F. to 233 F., or an aviation base stock gasoline boiling up to 190 F. and containing little, e. g. not more than about 4% aromatics.

The preparation of sulfurized saturated or unsaturated cyclic ketone reaction products of this invention is relatively simple and requires no elaborate or special equipment, undue precautions or skill. The obtainment of the desired reaction products simply requires a mixing and stirring of cyclic ketones of this invention with for example, elemental sulfur in an inert atmosphere, such as nitrogen or carbon dioxide, for 2 to 8 hours. Initially the reaction is kept at between about 60 C. and about 80 C., the mixture being then rapidly heated to an elevated temperature of 200 C., or higher. At the completion of the reaction the desired fraction may be extracted with a nonaromatic hydrocarbon having a boiling point of 164 F. to 233 F. The non-extractable material is discarded and the solution is filtered, evaporatedatstea temp ture i a cu rent; of iner rated in a current of carbon dioxide.

gas to yield the desired products suitable as lubricant additives. The additives thus produced vary in color from amber to dark brown and in consistency from viscous liquid to brittle solids. They are readily soluble in various petroleum lubricating oils as well as other types of oleaginous materials, oils and synthetic lubricating bases. 7

The sulfurized cyclic ketones of this invention may be neutralized by treating the reaction product with a suitable basic compound such as a hydroxide, carbonate or oxide of an alkaline earth metal, alkali metal or other suitable basic reagents such as ammonia, alkyl or aryl substituted ammonia such as amines or the reaction products may be treated with heavy metals such as Al, Cr, Fe, Fn and the like. Preferred reagents are Ca, Ba, Mg, Na, K, Al and Zn.

The general procedure for preparing the neutralized reaction products of this invention may be attained by dispersing or dissolving for example a sulfur treated cyclic ketone in a large quantity of a suitable hydrocarbon oil by heating under oxidizing conditions such as blowing air, oxygen, etc. through the blend at approximately steam temperature. To this composition a calculated amount of lime or, any other desired neutralizing agent may be added and the mixture agitated at an elevated temperature of above C. for over a period ,of 2 hours. After the reaction is completed a stream of inert gas is introduced to remove any entrained moisture or other contaminants. The neutralized sulfur-cyclic ketone reaction product is then filtered to recover the product from the oil and may be refiltered to remove excess lime and other impurities.

To more clearly illustrate the present invention, the following examples are presented. It is to be understood, however, that various modifications can be resorted to without departing from the spirit of the invention as presented in the subjoined claims.

EXAMPLE I A mixture of approximately one mol of cyclic unsaturated ketones containing at least 18 carbon atoms in the molecule, obtained by topping bottoms from crude isophorone bottoms at a kettle temperature of between about and 10 mm. Hg pressure, and about one-half mol of sulfur was stirred and heated in an inert atmosphere of carbon dioxide for approximately 24 hours at around about C. At the end of the reaction period, the desired product was extracted with a non-aromatic hydrocarbon having a boiling range of between about 164 F. and 233 F. The solution was filtered and the filtrate evapo- The sulfurized cyclic ketone was readily soluble in mineral oil and was non-corrosive 'to a copper strip test.

EXAMPLE II A mixture of approximately one mol of cyclic unsaturated ketones having between about 12 and 15 carbon atoms in the molecule and derived from condensation of acetone in 30% to 60% caustic solution at a temperature ranging from about 130 to C. and under pressure of from 300 to 500 pounds per square inch, and about onehalf mol of elemental sulfur was stirred and heated in an inert atmosphere of carbon. dioxide for over 24 hours at around about 160 C. The reaction product was then extracted with a nonaromatic hydrocarbon as denoted in Example I. This reaction product was also soluble in mineral oil and is non-corrosivein the copper strip test,

A calcium salt" of the 'sulfurize'd' unsaturated cyclic "ketone'of Example Ilwas prepared in the followin manner. Approximately parts of the" reaction product of Example 'I was dissolved ina desired'amount' of mineral lubricating oil'by gentle heating ata'bo'ut .90 to 100 'C. and blend was a'ir blown. If desired this mixture may be filtered to remove any foreign and oil insoluble matter. To this heated mixture,,ab0ut parts of lime is added and the product heated for about 3"hours at about 100" C. The mixture is then filtered to remove excess lime and the filtrate reheated for about 2 hours at between 120 and 130C. A streamof nitrogen gas is thenblown through the mixture toremove-entrained foreign matter and moisture and the salt recovered from the oil solution. This calcium salt of sulfurized unsaturated cyclic ketone is readily soluble in mineral oil and is non-corrosive to a copper strip test.

The copper strip test was conducted by suspending a clean copper strip in a vessel containing mineral oil admixed withabout 0.3% of the reaction product of this invention.- This vessel is suspended over a vigorously boiling vessel of water for 3 hours. After this interval the copper strip is removed and observed whether it has darkened. Copper strips in oils inhibited with products as preparedin the above examples were not darkened but remained bright and'clean.

About-0.1% by weight of the reaction product of Example I in a mineral oil was subjected to a multiple-four-ball machine-test similar in principle to the Boerlage apparatus described in the magazine, Engineering volume 136, July 14, 1933. This apparatus comprises four steel balls arranged in pyramid formation. The top ball is rotated by spindlesagainst the-.three'bottom balls which are clamped in a stationary ball holder. The balls are immersed in the coil to be tested. Tests were run for two hours at 600 R. P. M. under 6 kg. load at controlled temperature as indicated in the table. The diameter of the wear scars worn on the three ballsforming the base of the pyramid'were measured, and the average taken as the true indication of wear.

Wear evaluation inthe multiple: four ball machine A refined, undoped lubricating oil, 64-67 SV at 210 F. was employed.

Scar Diameter in mm;

Additive Ammt Per cent 7 weight None S klfurized Product of Example combined .withiotheradditives inlubricantasuch as blooming agents, pour POiIltmdBPI'BSSfiHtSgQViSr cosity improvers,. extremeipressure' agents, antifoaming.ag.ents,.and the like. Among the specific additives-which :can be usedzare oil-solubledetergents which include oil-soluble salts of: various. bases with detergent-forming.acids. Such bases include metal as well as :organic bases. Metallimbasesinclude. the hydroxides, .etc. .ofzthe alkalizmetals, Cu, .Mg, Ca,.Sr, Ba, Zn, Cd, Al Sn, Pb, .Cr, Mn, Fe, Ni Co, .etc. Organic bases include variousnitrogenbases :as primary, secondary, tertiary and quaternary :amines.

Examples of detergent forming acids are the various fatty acids of, say 10 to 30 car-bon atoms, wool 'fat acids, parafiin wax acids (produced 'by oxidation of parafin wax), chlorinated fatty acids, rosin acids, aromatic carboxylic acids, including aromaticfatty acids, aromatic hydroxy fatty acids, parafiin wax benzoic-acids, various alkyl substituted salicyclic acids, phthalic acid and then monoesters, aromatic keto acids, aromatic ether acids; diphenols as'di-(alkyl phenol) sulfides and disulfides, methylene bis alkyl phenols; sulfonic acids such as may be'produced by treatment of alkyl aryl hydrocarbons or 'high boiling petroleum oils "with sulfuric acid monoesters; phosphoric; arsonic and antimony acid mono and diesters, including the corresponding thiophosphoric, arsonic and antimony acids; phosphoric and arsonic acid and they like.

Additional detergents are the alkaline earth phosphate diesters, 'including'the thiophosphate di-ester; the alkaline earth diphenolates, specifis cally the calcium and barium salts .of diphenol mono and poly sulfides.

Non-metallic detergents include compounds such as the phosphatides such as lecithin and caphalin, certain fatty oils as rapeseedoilsLvol- I talized fatty or mineral oils and the like.

An excellent metallic detergent .for the present purpose is the calcium salt of oil-soluble petroleumsulfonic acids. This may be present advantageously in the amount of about 0.025% to-0I2% sulfate ash. Also alkaline earth salts ,of alkyl pheno-aldehyde condensation reaction products are excellent detergents.

Anti-oxidants compriseseveral types, for example, alkyl phenols such as 2,4,6-trimetliy1 phenol, pentamethylphenol, 2,4 dimethyl 6- .tertiary butyl phenol, 2,4 dimethyl 6 octylphenol, 2,6-ditertiarybutyl-4 methyl phenol, 2,4,6-tritertiary-butyl phenol andthe'like; amino phenols as benzyl aminophenols; amines suchas dibutyl phenylene .diamine, diphenyl amine,

phenyl beta naphthylamine, phenyl alphanaphthylamine, dinaphthylamine.

Corrosion inhibitors or anti rusting compoundsmay also be present, such as dicarboxylic acids of 16 and more carbon atoms; alkali'metal and alkalineearth salts of 'sulfonic acids and fatty acids; organic compounds containing an acidic radical in close proximity to a nitrile, nitro or nitroso group (e. g. alpha cyano'stearic acid).

Extreme pressure agents that maybe used 'compr-isezesters of phosphorusacidssuch as triaryl, alkyl hydroxy aryl, or aralkyl phosphates, thiophosphates or phosphites and the like neu- 'tral aromatic sulfur compounds of relatively high boiling temperatures such as diaryl sulfides,- diaryl disulfides, alkyl aryldisulfides, e. g. diphenyl sulfide, diphenol sulfide, dicresol sulfide, dixylenol. sulfide, methyl butyl diphenol sulfide, dibenzyl sulfide, corresponding -di-- and tri sulfides, andthe like; sulfurized fatty oils or esters of fatty acids and monohydric alcohols; e. g sperm oil, jojoba oil, etc., inwhich the sulfur isallophanates, carbazides, carbazones, etc.; polyisobutylene polymers, unsaturated polymerized esters of fatty acids and monohydric alcohols and other high molecular weight oil-soluble compounds.

Depending upon the additive used and conditions under which it is used, the amount of additive used may vary from 0.01 to 2% or higher.

However, substantial improvement is obtained by using amounts ranging from 0.1 to 0.5% in combination with sulfurized cyclic ketone reaction products of this invention.

It is to be understood that while the features of the invention have been described and illustrated in connection with certain specific examples, the invention, however, is not to be limited thereto or otherwise restricted, except by the prior art and the scope of the appended claims.

I claim as my invention?- 1. A lubricating oil composition of matter comprising a major amount of an oleaginous material and a minor amount, suflicient to stabilize said oleaginous material against deterioration and to improve its anti-wear properties, of a stable non-corrosive product of the group of a sulfur-containing and a metal salt of sulfurcontaining reaction product obtained by reacting, at an elevated temperature of from about 130 to about 200 C., for from 2 to 8 hours, a cyclic ketone fraction having at least 12 carbon atoms with a non-phosphorus containing sulfurizing agent.

2. A lubricating oil composition comprising a major amount of an oleaginous material and a minor amount, sufficient to stabilize said oleaginous material against deterioration and improve its anti-wear properties, of a stable, noncorrosive sulfur-containing reaction product obtained by reacting, at an elevated temperature of from about 130 to about 200 C. for from 2 to 8 hours, a cyclic ketone fraction having at least 12 carbon atoms with a non-phosphorus containing sulfurizing agent.

3. A lubricating oil composition comprising a major amount of an oleaginous material and a minor amount, sufficient to stabilize said oleaginous material against deterioration and improve its anti-wear properties, of a stable, noncorrosive sulfur-containing reaction product obtained by reacting, at an elevated temperature of from about 130 to about 200 C. for from 2 to 8 hours, unsaturated cyclic ketone fraction having at least 12 carbon atoms with a non-phosphorus containing sulfurizing agent.

4. A lubricating oil composition comprising a major amount of an oleaginous material and a minor amount, but suificient to stabilize said oleaginous material against deterioration and improve its anti-wear properties, of a stable, noncorrosive sulfur-containing reaction product ob-- tained by reacting, at an elevated temperature of from about to about 200 C. for from 2' to 8 hours, unsaturated cyclic ketone fractions having at least 12 carbon atoms and derived from condensation of acetone to high molecular weight isophorone type fractions with a non-phosphorus containing sulfurizing agent.

5. A lubricating composition comprising a ma 200 C. for from 2 to 8 hours, isophorone bottoms comprising essentially unsaturated cyclic ketone fractions having at least 12 carbon atoms with a non-phosphorus containing sulfurizing agent.

6. A lubricating composition comprising a major amount of a mineral lubricating oil and 9 minor amount, but sufiicient to stabilize said mineral oil against deterioration and improve its anti-wear properties, of a stable, non-corrosive sulfur-containing reaction product obtained by reacting, at an elevated temperature of from about 130 to about 200 C. for from 2 to 8 hours, crude isophorone bottoms comprising essentially unsaturated cyclic 'ketone fractions having at least 15 carbon atoms per molecule with a nonphosphorus containing sulfurizing agent.

'7. A lubricating composition comprising a major amount of a mineral lubricating oil and a minor amount, but sufiicient to stabilize said: mineral oil against deterioration and improve its anti-wear properties,'of a stable, non-corrosive sulfur-containing reaction product obtained by reacting, at an elevated temperature of from about 130 to 200 C..for. from 2 to 8'hours, crude hydrolyzed isophorone bottoms comprising essentially unsaturated cyclic ketone fractions having at least 15 carbon atoms per molecule with non- 1 phosphorus containing sulfurizing agent.

8. A lubricating composition comprising a major amount of a mineral lubricating oil and a minor amount, but suificient to stabilize said mineral oil against deterioration and improve its anti-wear properties, of a stable, non-corrosive sulfur-containing reaction product obtained by reacting, at an elevated temperature of from about 130 to about 200 C. for from 2 to 8 hours, crude isophorone bottoms comprising essentially unsaturated cyclic ketone fractions having at least 15 carbon atoms per molecule with sulfur.

9. A composition of matter comprising a major amount of an oleaginous material and a minor amount, suflicient to stabilize said oleaginous material against deterioration and improve its antiwear properties, of a stable, non-corrosive metal salt of a sulfur-containing reaction product obtained by reacting, at an elevated temperature of from about 130 to about 200 C. for from 2 to 8 hours, a cyclic ketone fraction having at least 12 carbon atoms with a sulfurizing agent.

10. A composition of matter comprising a major amount of an oleaginous material and a minor amount, suflicient to stabilize said oleaginous material against deterioration and improve its anti-wear properties, of a stable, non-corrosive metal salt of a sulfur-containing reaction product obtained by reacting, at an elevated temperature of from about 130 to about 200 C. for from 2 to 8 hours, unsaturated cyclic ketone fracas tsw tionlhavingaat leastrl2soaiebon atoms with anon phosphorus. containing?sulfurizingnagent.l.

11-..lA' ico-r npositionaof matter born-prising a .m-a-- jonamou-n-t ofan oleaginousmaterial and a minor.

amount butasumcienteto zstabl-i-ze said oleaginousi material against. deterioration and. improve: its antiawear properties; ot a stable; .non-corrosive metaLsal-t of vasulfun-zcontaining reaction product obtained by reacting,- atan elevated temperatureofi-rom aboutl-30l to aboutZOO-P C.-for from 2 to 8 hours;unsatuitatedacyclicsketone fractions havingatileasta 12 carbon atomssand derivedfrom voondensation of: acetone to: high molecular weight isophorone' type fractions with. a non-phosphorus containing sul-furizingl agent.

12.! .A lubricating composition comprising. ama-w 1 01% amountaof. a-mineralrlubricating oiland a minoramount;--. but sufficient to stabilize said.

mineral oil against deterioration and improve: its:

anti-wear properties; .of .-a stable, metal salt ofa.

sulfur-containing: reaction product obtained by reacting at an-elevatedrtem-perature of from about 130 3 to aboutn200f G..fo1=;-from.- 2: to 8-hours, iso--- phonone bottoms comprising! essentially unsaturatedcyclic;ketonedractionsshavings at least :12 carbon atoms with-a non-phosphorus .-contai-ning sulturizingragentr 1:32. A lubricating composition comprising :ama.-

jorr amount of a-=mineral, lubricating. oil anda.-. minor amount,-- but su-fiicient =to-- stabilize said, mineral oil. zagamstdetenioration: and. improve: its

anti-wean properties; ofa -stabie';- non-corrosive. calcium S31E01? asulfureoontainingi ireaotion prodnot obtained byareaotin'g; at-anelevated tempera? tureof zf romuabout 1305 to..about.200.".- C. .for from.

2 .to fitho-urs, .crude'isophorone bottomsrcompris ingr essentially amsatu xated. cyclioketone fractions having, atleast carbon atoms. penmolecule with sulfun. 1

14.. A lubticating composition comprising a ma.-.-

join. amount 1 of a .minenal'l lubricating 01mm... a. minor. amount, but s'ufiicientito.stabilizelsaid 'mi-ner'al oil fagainstd'etiio'ratidn and improve its anti-. wear properties, offa, stab1e}.non\-corrosive cal-1 40* Number- 12 onl I asalt ofa sulfurroontaininggreaotionproduct obtained. by,reacting atnartemperature of. from. 1308 ton200f -C.--fot from 2 to :8- hours, crude-.150. plaorone .bottoms comprisingessentially unsatue rated cyc1ic..-ketone. fractions having-T at least :12.

- atoms .andxlerivedL-ftom condensation.ofaacetonea to high molecular weight isophorone type. fracationswith about one-halfmolof sulfur.

17. As. a .composition,. ,a sulfurized'unsaturated-E cyclic.ketoneiraction :having .at -leastu12 carbon-iatoms. derived fromtheecondensation of acetone:

18 As. a. com-position,. .a: lsulfunized unsaturated: cyclic .ketone .fractionhavinge at least .-.12 carbon. atoms in the molecule...

19.. As a..composition,- a metal salt of a sulfurized. unsaturated..cyolicvketone. fractionihavinga at. least 12 .carbon.atoms in the molecule PAUL RHVANJESS;

REFERENCES CITED The following references'sare-of: record' imthe file-wof this: 'patentz 1 STATES PATENTS Name Date Pr-utton; .May-, 1941- OttO.6tEa1'.f Aug-.- 28, 1'945 2349,5186: Ottoet a1.. Apr.- 29,-51941- Certificate of Correction Patent No. 2,487,840 November 15, 1949 PAUL R. VAN ESS It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 10, line 40, before 200 C. insert the word. about;

and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 9th day of May, A. D. 1950.

THOMAS F. MURPHY,

Assistant Oommiaaioner of Paton'ta. 

